The invention relates to compounds of formula

wherein n is 1 or 3;

R is -N(R ₁ )R ₂ or -(O) _m R ₃ ; m is O or l;

R _j and R ₂ are each independently of the other H or an organic radical or, together with the nitrogen atom carrying them, form a heterocyclic radical containing at least one nitrogen atom; R ₃ is an organic radical; R ₄ is H or Cι-C ₆ alkyl; and X is fluorine or chlorine; in free form or in salt form, to a process for the preparation of those compounds and to the use of those compounds, to pesticidal compositions comprising an active ingredient selected from those compounds, in free form or in agrochemically acceptable salt form, to a process for the preparation of those compositions and to the use of those compositions, to plant propagation material treated with those compositions, to a method of controlling pests, to intermediates for the preparation of those compounds and to a process for the preparation of those intermediates and to the use of those intermediates.

In the literature, certain dihalocyclopropyl derivatives are proposed as active ingredients of pesticides. The biological properties of those known compounds are not entirely satisfactory in the field of pest control, however, and there is therefore a need to provide further compounds having pesticidal properties, especially for controlling insects and representatives of the order Acarina. That problem is solved according to the invention by the provision of the present compounds I.

The compounds I may partially be present in the form of tautomers; for example the compounds I, wherein R ₄ is hydrogen, may be present in equilibrium with the tautomers that contain an R-S(=O) ₂ -N=C(OH)- grouping instead of the R-S (=O) ₂ -N(H)-C(=O)- grouping. Accordingly, hereinbefore and hereinafter compounds I are to be understood to

include corresponding tautomers, although the latter are not specifically mentioned in every case.

The compounds I are capable of forming salts with bases. Suitable salts with bases are, for example, metal salts, such as alkali or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as mor- pholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or tri-hydroxy-lower alkyl¬ amine, for example mono-, di- or tri-ethanolamine. Agrochemically advantageous salts are preferred within the scope of the invention, but salts that have drawbacks as regards agrochemical uses, for example salts that are toxic to bees or fish, are also included, such salts being used, for example, for the isolation and/or purification of free compounds I or the agrochemically acceptable salts thereof. Owing to the close relationship between the compounds I in free form and in the form of their salts, hereinbefore and hereinafter any reference to the free compounds I or the salts thereof should be understood as including the corresponding salts or the free compounds I, respectively, where appropriate and expedient. The same applies in the case of tautomers of compounds I and the salts thereof. In each case the free form is generally preferred.

Unless otherwise defined, the general terms used hereinbefore and hereinafter have the meanings given below:

An organic radical is preferably unsubstituted or substituted, e.g. mono- to tri-substituted, C _r C ₂₀ alkyl, the substituents being selected from the group consisting of halogen, C ₃ -C ₈ cycloalkyl, cyano, C _r C ₆ alkoxy, C _j -Cealkylthio, C _r C ₆ alkoxycarbonyl, C _r C ₄ alkylcarbonyl, C _r C ₄ alkoxy-C _r C ₆ alkoxy, C _j -Cgalkylcarbonyloxy, C _r C ₆ alkoxycarbonyloxy, aryl and, e.g. mono- to tri-substituted, aryloxy; unsubstituted or substituted, e.g. mono- to tri-substituted, C ₃ -C ₈ cycloalkyl, the substituents being selected from the group consisting of halogen and C _r C ₃ alkyl; C ₂ -C ₂₀ alkenyl; halo-C ₂ -C ₂₀ -alkenyl; C ₂ -C ₂₀ alkynyl; halo-C ₂ -C ₂₀ -alkynyl; an unsubstituted or mono- to penta-substituted phenyl or naphthyl group, their substituents being selected from the group consisting of halogen, C _r C ₆ alkyl, C _r C ₆ haloalkyl, C _r C ₆ alkoxy, C _r C ₆ haloalkoxy, C _r C ₆ alkoxycarbonyl, C _r C ₆ alkylthio, cyano, nitro, aminosulfonyl, C _r C _f) alkylsulfonyl, C ₁ -C ₆ alkylsulfinyl and unsubstituted or mono- to penta-substituted phenyl, phenoxy or phenylthio residues, the substituents of these

residues being selected from the group consisting of halogen and C _r C ₄ alkyl, nitro, cyano and halo-C _r C ₄ alkyl.

Aryl - as a group per se and as a structural unit of other groups and compounds, such as aryloxy - is an unsubstituted or mono- to penta-substituted phenyl or naphthyl group, the substituents being selected from the group consisting of halogen, C ₁ -C ₆ alkyl, C _j -C ₆ alkoxy, phenoxy, cyano, nitro, C _r C ₄ haloalkyl, C _r C ₆ haloalkoxy, aminosulfonyl, C _r C ₆ alkoxycarbonyl and C _r C ₆ alkylthio.

An heterocyclic radical -N(R ₁ )R ₂ , containing at least one nitrogen atom in the ring system, is preferably an unsubstituted or mono- to tri-substituted, more preferably one- or disubstituted, saturated or unsaturated three- to seven-membered ring, containing if desired - besides the nitrogen atom contained in the formula -N(R,)R ₂ - one to three further ring heteroatoms, selected from the group consisting of N, O and S, and provided if desired with a fused-on benzene ring, the substituents of the heterocyclic residue being selected from the group consisting of halogen, C ₁ -C ₄ alkyl, C _r C ₄ alkoxycarbonyl, pyridyl, benzyl and unsubstituted or mono- to penta-substituted phenyl, the substituents of the phenyl residue being selected from the group consisting of halogen, C _r C ₄ alkyl, C _j -C ₄ alkoxy and nitro. For example, the radicals R _j and R ₂ may together form a straight- chained C ₃ -C ₆ alkylene group or an oxa-C ₂ -C ₅ alkylene group bonded via carbon atoms. Preference for the heterocyclic groups -N(R _j )R ₂ is given within the scope of the invention to piperidyl, morpholinyl, thiomorpholinyl, pyrrolidinyl, pyrrolyl, 4-methylpiperazinyl, 2,6-dimethylpiperidyl, 4-phenylpiperazinyl, 4-(4-fluorophenyl)-piperazinyl, 4-(2-methylphenyl)-piperazinyl, 4-(2-methoxyphenyl)-piperazinyl, 4-(4-methoxyphenyl)- piperazinyl, 4-(4-nitrophenyl)-piperazinyl, 4-(3,4-dichlorophenyl)-piperazinyl, 4-pyridylpiperazinyl, 4-ethylpiperazinyl, 4-benzylpiperazinyl, ,3-dimethylpiperidyl, 3-ethoxycarbonylpiperidyl, 4-ethoxycarbonylpiperidyl, 2,6-dimethylmorpholinyl, 2,6-din.ethylthiomorpholinyl, ,2,3,4-tetrahydroquinolinyl, 1 ,2,3,4-tetrahydroisoquinolinyl and indolinyl, which are preferably bonded to the sulfonyl group shown in formula I via the (or one of the) ring-nitrogen atom(s).

Halogen - as a group per se and as a structural unit of other groups and compounds, such as haloalkyl, haloalkenyl, haloalkynyl and haloalkoxy - is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine.

Unless otherwise defined, carbon-containing groups and compounds each contain from 1

up to and including 20, preferably from 1 up to and including 18, especially from 1 up to and including 10, more especially from 1 up to and including 6, especially from 1 up to and including 4, more especially from 1 up to and including 3, and above all 1 or 2, carbon atoms.

Alkyl - as a group per se and as a structural unit of other groups and compounds, such as alkylthio, alkylcarbonyl, alkoxyalkoxy, alkylcarbonyloxy, alkoxycarbonyloxy, alkylsulfonyl, alkylsulfinyl, haloalkyl, alkoxy, haloalkoxy and alkoxycarbonyl - is, in each case taking due account of the number of carbon atoms present in the group or compound in question, either straight-chained, for example methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-hexadecyl or n-octadecyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.

Alkenyl, haloalkenyl, alkynyl and haloalkynyl are straight-chained or branched and contain in each case two or, preferably, one unsaturated carbon-carbon bond(s). The double or triple bonds of these substituents are preferably separated from the remaining part of the compound I by at least one saturated carbon atom. Examples which may be mentioned are allyl, methallyl, but-2-enyl, but-3-enyl, propargyl, but-2-ynyl and but-3-ynyl.

Halo-substituted carbon-containing groups and compounds, such as haloalkyl, haloalkenyl, haloalkynyl and haloalkoxy, may be partially halogenated or perhalogenated, it being possible in the case of multiple halogenation for the halogen substituents to be identical or different. Examples of haloalkyl - as a group per se and as a structural unit of other groups and compounds, such as haloalkoxy - are methyl mono- to tri-substituted by fluorine, chlorine and/or by bromine, such as CHF ₂ , CF ₃ or CH ₂ C1; ethyl mono- to penta- substituted by fluorine, chlorine and/or by bromine, such as CH ₂ CF ₃ , CF ₂ CF ₃ , CF ₂ CC1 ₃ , CF ₂ CHC1 ₂ , CF ₂ CHF ₂ , CF ₂ CFC1 ₂ , CH ₂ CH ₂ C1, CF ₂ CHBr ₂ , CF ₂ CHC1F, CF ₂ CHBrF or CC1FCHC1F; propyl or isopropyl mono- to hepta-substituted by fluorine, chlorine and/or by bromine, such as CH ₂ CHBrCH ₂ Br, CF ₂ CHFCF ₃ , CH ₂ CF ₂ CF ₃ , CF ₂ CF ₂ CF ₃ , CH(CF ₃ ) ₂ or CH ₂ CH ₂ CH ₂ C1; and butyl mono- to nona-substituted by fluorine, chlorine and/or by bromine, or one of the isomers thereof, such as CF(CF ₃ )CHFCF ₃ , CF ₂ (CF ₂ ) ₂ CF ₃ or CH ₂ (CF ₂ ) ₂ CF ₃ . Examples of haloalkenyl are 2,2-difluoroethen-l-yl, 2,2-dichloro- ethen-1-yl, 2-chloroprop-l-en-3-yl, 2,3-dichloroprop-l-en-3-yl and 2,3-dibromoprop-l-en-3-yl. Examples of haloalkynyl are 2-chloroprop-l-yn-3-yl, 2,3-dichloroprop-l-yn-3-yl and 2,3-dibromo-l-yn-3-yl.

Straight-chained C ₃ -C ₆ alkylene is trimethylene, tetramethylene, pentamethylene or hexa- methylene.

Straight-chained oxa-C ₂ -C ₅ alkylene bonded via carbon atoms is -CH ₂ -O-CH ₂ -, -CH ₂ -O-CH ₂ -CH ₂ -, -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -, preferably -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, preferably cyclopropyl or cyclohexyl.

Pyridyl is pyrid-3-yl, pyrid-4-yl or, preferably, pyrid-2-yl.

Preferred forms within the scope of the invention are:

(1) a compound of formula I wherein n is 1 or 3, especially 1;

(2) a compound of formula I wherein m is 0 or 1, especially 0;

(3) a compound of formula I wherein R is -N(R ₁ )R ₂ or -(O) _m R ₃ ; m is 0 or 1;

R _j and R ₂ are are each independently of the other H or an organic radical or, together with the nitrogen atom carrying them, form a heterocyclic radical containing at least one nitrogen atom; and R ₃ is an organic radical;

(4) a compound of formula I wherein R is -N(R _! )R ₂ and

R _j and R ₂ are each independently of the other H or an organic radical or, together with the nitrogen atom carrying them, form a heterocyclic radical containing at least one nitrogen atom; especially R, and R ₂ each independently of the other H; unsubstituted or mono- to tri-substituted C _j -C ₂ oalkyl, the substituents being selected from the group consisting of halogen, C ₃ -C ₅ cycloalkyl, cyano, C _r C ₆ alkoxy and

phenyl; unsubstituted C ₃ -C ₈ cycloalkyl; unsubstituted C ₃ -C ₂₀ alkenyl; or unsubstituted or mono- to tri-substituted phenyl, the substituents being selected from the group consisting of halogen, C _j - haloalkyl, C _r C ₆ alkoxy, cyano and nitro; or together with the nitrogen atom carrying them form an unsubstituted or mono- or di-substituted three- to six-membered ring containing if desired - besides the nitrogen atom shown in the formula -N(Rι)R ₂ - a further hetero atom from the group consisting of N, O and S, the substituents being selected from the group consisting of C ₁ -C ₄ alkyl, benzyl, pyridyl, C _j - alkoxycarbonyl and unsubstituted or mono- to tri-substituted phenyl residues, the substituents of these residues being selected from the group consisting of halogen, C _r C ₄ alkyl, C _r C ₄ alkoxy and nitro;

(5) a compound of formula I wherein R is -(O) _m R ₃ ; m is O or 1; and

R ₃ is an organic radical; especially C ₁ -C ₂₀ alkyl; halo-C _r C ₆ alkyl; unsubstituted or mono- to penta-substituted phenyl or naphthyl, the substituents being selected from the group consisting of halogen, C _r C ₆ alkyl, Cι-C ₆ haloalkyl, C _r C ₆ alkoxy, C _r C ₆ haloalkoxy, Ci-Cgalkoxycarbonyl, C _r C ₆ alkylthio, cyano, nitro, aminosulfonyl, C _r C ₆ alkylsulfonyl, Cι-C ₆ alkylsulfinyl, phenyl and phenoxy; or benzyl;

(6) a compound of formula I wherein R ₄ is H or C _r C ₆ alkyi; especially H;

(7) a compound of formula I wherein

R is C _r C ₂ oalkyl; halo-Cι-C ₂₀ alkyl; -NCR^R^ an unsubstituted or mono- to penta- substituted phenyl or naphthyl group, the substituents being selected from the group consisting of halogen, C _r C ₆ alkyl, halo-C _r C ₄ alkyl, C _r C ₆ alkoxy, halo-C _r C ₄ - alkoxy, cyano, nitro and C _r C ₆ alkoxycarbonyl; or an unsubstituted or mono- to tri- substituted benzyl or biphenylyl group, the substituents being selected from the group consisting of halogen and nitro, and a substituted benzyl group being substituted at its phenyl partial structure; and

R, and R ₂ are each independently of the other C _r C ₄ alkyl or together form a straight- chained C ₃ -C ₆ alkylene group or a straight-chained oxa-C ₂ -C ₅ alkylene group bonded via carbon atoms; wherein, especially,

R is Cι-C ₁₈ alkyl; ha-0-C..- alkyl; -N(R ₁ )R ₂ ; an unsubstituted or mono- to penta- substituted phenyl or naphthyl group, the substituents being selected from the group consisting of halogen, C ₁ -C ₆ alkyl, halo-C _r C ₄ alkyl, C _r C ₆ alkoxy, halo-C _r C ₄ - alkoxy, cyano, nitro and C _r C ₆ alkoxycarbonyl; or an unsubstituted benzyl or biphenylyl group; and

R _j and R ₂ are each independently of the other C _r C ₄ alkyl or together form a straight- chained oxa-C ₂ -C ₅ alkylene group bonded via carbon atoms; wherein, more especially,

R is Cι-C ₆ alkyl; halo-C _r C ₄ alkyl; -N(R,)R ₂ ; unsubstituted naphthyl; unsubstituted or mono- to tri-substituted phenyl, the substituents being selected from the group consisting of halogen, C _r C ₆ alkyl, halo-C _r C ₂ alkyl, C _r C ₆ alkoxy, halo-C _r C ₄ - alkoxy, cyano, nitro and C _r C ₄ alkoxycarbonyl; or an unsubstituted benzyl or biphenylyl group; and

Rj and R ₂ are each independently of the other C _r C ₂ alkyl or together form a straight- chained oxa-C ₃ -C ₅ alkylene group bonded via carbon atoms; wherein, especially,

R is C _r C ₆ alkyl; -N(R,)R ₂ or unsubstituted or mono- to tri-substituted phenyl, the substituents being selected from the group consisting of halogen, C _j -C ₆ alkyl, halo- C _r C ₂ alkyl, C _r C ₆ alkoxy, halo-C _r C ₄ alkoxy, cyano, nitro and C _r C ₄ alkoxycarbonyl; and

Rj and R ₂ together form a straight-chained oxa-C ₃ -C ₅ alkylene group bonded via carbon atoms; wherein, more especially,

R is C _r C ₄ alkyl; -N(Rj)R ₂ or unsubstituted or mono- or di-substituted phenyl, the substituents being selected from the group consisting of halogen, C _j -C alkyl, halo- C ₁ -C ₂ alkyl, C _r C ₄ alkoxy, halo-C _r C ₂ alkoxy, cyano, nitro and C _r C ₂ alkoxycarbonyl; and

R _j and R ₂ together form a straight-chained oxa-C ₄ -C ₅ alkylene group bonded via carbon atoms; wherein, very especially,

R is C _j -C ₄ alkyl; morpholinyl; or phenyl that is unsubstituted or mono-substituted by halogen, halo-C _j -C ₂ alkyl or by nitro; wherein, above all,

R is C _j -C alkyl; morpholin-4-yl; or phenyl that is unsubstituted or mono-substituted by chlorine, trifiuoromethyl or by nitro;

(8) a compound of formula I wherein

X is fluorine or chlorine, especially fluorine;

(9) a compound of formula I wherein n is 1 or 3;

R is C _j -C ₁₈ alkyl; benzyl; an unsubstituted or mono- to tri-substituted phenyl or naphthyl group, the substituents being selected from the group consisting of halogen, C _j -C ₆ alkyl, halo-C _j - alkyl, and nitro; an unsubstituted or mono- or di-substituted morpholinyl or thiomorpholinyl group; or -N(R _j ) R ₂ ;

R _j and R ₂ are each independently of the other H; unsubstituted or mono- or di-substituted C _j -C ₆ alkyl, the substituents being selected from the group consisting of C ₃ -C ₅ cycloalkyl and C _j -C ₆ alkoxy; C ₃ -C ₈ -cycloalkyl; benzyl; or C ₃ -C ₆ alkenyl; or R _j and R ₂ together form a straight-chained C ₃ -C ₆ alkylene group;

X is fluorine; and

R ₄ is H;

(10) a compound of formula I wherein n is 1 or 3;

R is C _j -C ₁₈ alkyl; halo-C _j -C ₄ alkyl; -N(R _j )R ₂ ; an unsubstituted or mono- to penta- substituted phenyl or naphthyl group, the substituents being selected from the group consisting of halogen, C -C ₆ alkyl, halo-C _j -C ₄ alkyl, C _r C ₆ alkoxy, halo-C _j -C ₄ - alkoxy, cyano, nitro and C -C ₆ alkoxycarbonyl; or benzyl or biphenylyl;

R _j and R ₂ are each independently of the other C _j -C ₄ alkyl or together form a straight- chained oxa-C ₂ -C ₅ alkylene group bonded via carbon atoms;

X is fluorine; and

R ₄ is H;

(11) a compound of formula I wherein n is 1 or 3;

R is C _j - alkyl; -N(R _j )R ₂ or unsubstituted or mono- or di-substituted phenyl, the substituents being selected from the group consisting of halogen, C _j -C ₄ alkyl, halo- C _j -C ₂ alkyl, C _j -C ₄ alkoxy, halo-C _r C ₂ alkoxy, cyano, nitro and C _j -C ₂ alkoxycarbonyl;

R _j and R ₂ together form a straight-chained oxa-C ₄ -C ₅ alkylene group bonded via carbon atoms;

(12) a compound of formula I wherein n is 1;

R is C -C ₄ alkyl; morpholinyl; or phenyl that is unsubstituted or mono-substituted by halogen, halo-C -C ₂ alkyl or by nitro; X is fluorine; and R ₄ is H;

(13) a compound of formula I wherein n is 1;

R is C _j -C ₄ alkyl; morpholin-4-yl; or phenyl that is unsubstituted or mono-substituted by chlorine, trifluoromethyl or by nitro; X is fluorine; and R ₄ is H.

Special preference is given within the scope of the invention to the compounds of formula I listed in Examples PI and P2.

Within the scope of the invention, preference is given specifically to: N-[(2,2-difluoro- cyclopropyl)acetyl]-4-chlorobenzenesulfonamide, N-[(2,2-difluorocyclopropyl)acetyl]- benzenesulfonamide and N-[(2,2-difluprocyclopropyl)acetyl]-4-morpholinesulfonamide.

Very special preference is given within the scope of the invention to N-[(2,2-difluoro- cyclopropyl)acetyl]-benzenesulfonamide.

The invention relates also to a process for the preparation of the compounds of formula I, in free form or in salt form, which comprises, for example,

a) reacting a compound of formula

which is known or can be prepared analogously to corresponding known compounds and wherein n and X are as defined for formula I and Y is a leaving group, where appropriate

in the presence of a base, an acid catalyst or a water-binding agent, with a compound of formula

- Z

II / R- s -N (πi),

O ^K 4 which is known or can be prepared analogously to corresponding known compounds and wherein R and R ₄ are as defined for formula I and Z is hydrogen or an alkali metal atom, or

b) reacting a compound of formula

wherein R, R ₄ and n are as defined for formula I, or a salt thereof, in an inert solvent, with difluorocarbene or chlorofluorocarbene and/or, if desired, converting a compound of formula I obtainable in accordance with the process or by a different method, in free form or in salt form, into a different compound of formula I, separating a mixture of isomers obtainable in accordance with the process and isolating the desired isomer and/or converting a free compound of formula I obtainable in accordance with the process or by a different method into a salt or converting a salt of a compound of formula I obtainable in accordance with the process or by a different method into the free compound of formula I or into a different salt.

The remarks made above in relation to tautomers and/or salts of compounds I apply analogously to the starting materials listed hereinbefore and hereinafter as regards the tautomers and/or salts thereof.

The reactions described hereinbefore and hereinafter are carried out in a manner known per se, for example in the absence or, where appropriate, in the presence of a suitable solvent or diluent or of a mixture thereof, the reaction being carried out as required with cooling, at room temperature or with heating, for example in a temperature range from approximately -80°C to the boiling temperature of the reaction mixture, preferably from approximately -20°C to approximately +150°C, and, if necessary, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions. Especially

advantageous reaction conditions can be found in the Examples.

The starting materials given hereinbefore and hereinafter that are used for the preparation of compounds I, in free form or in salt form, are known or can be prepared in accordance with methods known per se, for example in accordance with the instructions given below, and insofar as they are novel, the invention relates also thereto.

Variant a):

Suitable leaving groups Y in compounds II are, for example, hydroxy, Cj-C ₈ alkoxy, halo-Cj-C ₈ alkoxy, C _j -C ₈ alkanoyloxy, mercapto, C C ₈ alkylthio, halo-C _j -C ₈ alkylthio, C _j -C ₈ alkanesulfonyloxy, halo-C _r C ₈ alkanesulfonyloxy, benzenesulfonyloxy, toluene¬ sulfonyloxy and halogen. Preference is given to C _j -C ₈ alkoxy and halogen, especially chlorine and bromine, very especially chlorine.

Suitable alkali metal atoms Z in compounds III are, for example, lithium, sodium and especially potassium atoms.

Suitable bases for facilitating the HY removal (where Y = alkanesulfonyloxy, haloalkane- sulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy or halogen) are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbon¬ ates, dialkylamides or alkylsilylamides or alkylamines, alkylenediamines, unsubstituted or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. The following may be mentioned by way of example: sodium hydroxide, hydride, amide, methanolate, acetate or carbonate, potassium tert- butanolate, hydroxide, carbonate or hydride, lithium diisopropylamide, potassium bis(tri- methylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylene- diamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyl-tri- methylammonium hydroxide and l,5-diazabicyclo[5.4.0]undec-5-ene (DBU).

Suitable acid catalysts for facilitating the reaction are, for example, acid halides of mineral acids, such as SOCl ₂ , SO ₂ Cl ₂ , PC1 ₃ , PBr ₃ , PC1 ₅ and especially POCl ₃ .

Suitable water-binding agents for facilitating the HY removal (where Y = hydroxy) are, for example, carbodiimides, such as N,N'-dicyclohexylcarbodiimide, or l-alkyl-2-halo- pyridinium salts, such as l-methyl-2-chloropyridinium iodide.

The reactants can preferably be reacted with one another as such, i.e. without the addition of a solvent or diluent, preferably, for example, in the melt. The addition of an inert solvent or diluent or of a mixture thereof to the reaction mixture is, however, likewise possible and in many cases advantageous. Examples of such solvents or diluents that may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydro¬ carbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichloro- benzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, tri- chloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-di- methylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, bases used in excess, such as triethyl- amine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also be used as solvents or diluents. If the reaction is carried out in the presence of an acid catalyst, acids, for example strong organic carboxylic acids, such as unsubstituted or substituted, for example halo-substituted, C _j -C ₈ a_kanecarboxylic acids, for example unsubstituted or substituted formic, acetic or propionic acid, or the acid catalyst itself used in excess, may also be used as solvents or diluents.

The reaction is advantageously carried out in a temperature range from approximately -20°C to approximately +180°C, preferably from approximately +10°C to approximately +150°C, in many cases in the range from room temperature to the reflux temperature of the reaction mixture and, in the absence of a solvent or diluent, preferably at the melting temperature of the reaction mixture.

The water of reaction formed during the reaction of compounds II wherein Y is hydroxy can, where appropriate, be removed using a water separator, by azeotropic distillation or by the addition of a suitable molecular sieve.

Variant b:

Suitable inert solvents for the reaction of compounds IV with difluorocarbene or chloro- fluorocarbene are, for example, aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chloro- benzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; sulfoxides, such as dimethyl sulfoxide, and especially high-boiling ethers, such as diethyl- ene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme) or tetra- ethylene glycol dimethyl ether (tetraglyme).

The reaction is advantageously carried out in a temperature range from approximately -20°C to approximately +180°C, preferably from approximately +10°C to approximately +150°C, and in many cases in the range from room temperature to the reflux temperature of the reaction mixture.

The dihalocarbenes used in the reaction can be prepared in a manner known per se, prefer¬ ably in situ; chlorofluorocarbene can be prepared, for example, starting from an alkali metal dichlorofluoroacetate, such as sodium dichlorofluoroacetate, or a halochlorofluoro- hydrocarbon, such as dichlorofluoromethane, and difluorocarbene, for example, starting from an alkali metal chlorodifluoroacetate, such as sodium chlorodifluoroacetate, a halodi- fluorohydrocarbon, such as chlorodifluoromethane, an organotin compound, such as tri- fluoromethyl-trimethyl-tin, an organomercury compound, such as phenyl-trifluoromethyl- mercury, or an organophosphorus compound, such as difluoro-tris(trifluoromethyl)ph s- phorane or bromodifluoromethyl-triphenyl-phosphonium bromide.

The compounds IV used as starting materials in Process variant b), in free form or in salt form, are novel and the invention relates also thereto.

The invention relates also to a process for the preparation of the compounds of formula IV, in free form or in salt form, which comprises, for example,

c) reacting a compound of formula

which is known or can be prepared analogously to corresponding known compounds and wherein n is as defined for formula I and Y is a leaving group, where appropriate in the presence of a base, an acid catalyst or a water-binding agent, with a compound of formula

° Z

II R - S - N (πi),

O ^H 4 which is known or can be prepared analogously to corresponding known compounds and wherein R and R ₄ are as defined for formula I and Z is hydrogen or an alkali metal atom, for example in a manner analogous to that described in Variant a) for the corresponding reaction of a compound of formula II with a compound of formula III, and/or, if desired, converting a compound of formula IV obtainable in accordance with the process or by a different method, in free form or in salt form, into a different compound of formula IV, separating a mixture of isomers obtainable in accordance with the process and isolating the desired isomer and/or converting a free compound of formula IV obtainable in accordance with the process or by a different method into a salt or converting a salt of a compound of formula IV obtainable in accordance with the process or by a different method into the free compound of formula IV or into a different salt.

A compound I or IV obtainable in accordance with the process or by a different method can be converted in a manner known per se into a different compound of formula I or IV, respectively, by replacing one or more substituents of the starting compound I or IV in customary manner by (a) different substituent(s) according to the invention.

For example:

- in compounds I or IV having an unsubstituted phenyl radical R, substituents can be introduced into the phenyl radical R; or

- in compounds I or IV having an unsubstituted alkyl radical R, halogen substituents can be introduced into the alkyl radical R.

Depending on the choice of reaction conditions and starting materials suitable for each purpose, it is possible to replace only one substituent by another substituent according to

the invention in a reaction step, or to replace several substituents by other substituents according to the invention in the same reaction step.

Salts of compounds I and IV can be prepared in a manner known per se. For example, salts of compounds I and IV with bases are obtained by treatment of the free compounds with a suitable base or a suitable ion exchange reagent.

Salts of compounds I and IV can be converted into the free compounds I and IV, respect¬ ively, in customary manner: for example by treatment with a suitable acid or a suitable ion exchange reagent.

Salts of compounds I and IV can be converted into different salts of compounds I and IV, respectively, in a manner known per se.

Depending upon the procedure and the reaction conditions, compounds I and IV having salt-forming properties can be obtained in free form or in the form of salts.

The compounds I and IV, in free form or in salt form, may be in the form of one of the possible isomers or as a mixture thereof, for example according to the number of asymmetric carbon atoms occurring in the molecule and the absolute and relative config¬ uration thereof and/or according to the configuration of non- aromatic double bonds occurring in the molecule, they may be in v form of pure isomers, such as antipodes and/or diastereoisomers, or in the form of mixtures of isomers, such as mixtures of enantiomers, for example racemates, mixtures of diastereoisomers or mixtures of racemates; the invention relates both to the pure isomers and to all possible mixtures of isomers and this is to be understood hereinbefore and hereinafter, even if stereochemical details are not specifically mentioned in each case.

Mixtures of diastereoisomers and mixtures of racemates of compounds I and IV, in free form or in salt form, that are obtainable in accordance with the process depending upon the starting materials and procedures chosen, or by other means, can be separated into the pure diastereoisomers or racemates in known manner on the basis of the physicochemical differences between the constituents, for example by fractional crystallisation, distillation and/or chromatography.

Correspondingly obtainable mixtures of enantiomers, such as racemates, can be separated

inlo the optical antipodes by known methods, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbents, for example high- pressure liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilised enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, in which case only one enantiomer is complexed, or by conversion into diastereoisomeric salts and separation of the resulting mixture of diastereoisomers, for example on the basis of their different solubilities by fractional crystallisation, into the diastereoisomers from which the desired enantiomer can be freed by the action of suitable agents.

Apart from by the separation of corresponding mixtures of isomers, it is possible according to the invention to obtain pure diastereoisomers or enantiomers also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials having correspondingly suitable stereochemistry.

It is advantageous to isolate or synthesise the biologically more active isomer, for example enantiomer or diastereoisomer, or mixture of isomers, for example mixture of enantiomers or mixture of diastereoisomers, insofar as the individual components have different biological activity.

The compounds I and IV, in free form or in salt form, can also be obtained in the form of their hydrates and/or may include other solvents, for example solvents that may be used for the crystallisation of compounds in solid form.

The invention relates to all those forms of the process according to which a compound obtainable as starting material or intermediate at any stage of the process is used as starting material and all or some of the remaining steps are carried out, or a starting material is used in the form of a derivative or a salt and/or its racemates or antipodes or, especially, is formed under the reaction conditions.

In the process of the present invention there are preferably used those starting materials and intermediates, in each case in free form or in salt form, which result in the compounds I described at the beginning as being especially valuable, or their salts.

The invenϋon relates especially to the preparation processes described in Examples PI

to P4.

The invention relates also to starting materials and intermediates used according to the invention for the preparation of the compounds I or the salts thereof, in each case in free form or in salt form, that are novel, to a process for the preparation thereof and to their use as starting materials and intermediates for the preparation of the compounds I; this applies especially to compounds IV.

In the area of pest control, the compounds I according to the invention are valuable preventive and/or curative active ingredients having a very advantageous biocidal spectrum even at low rates of concentration, while being well tolerated by warm-blooded animals, fish and plants. The compounds of the invention are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects and representatives of the order Acarina. The insecticidal or acaricidal action of the compounds of the invention may manifest itself directly, i.e. in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or indirectly, for example in reduced oviposition and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60 %.

The mentioned animal pests include, for example: of the order Lepidoptera, for example,

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.; of the order Coleoptcra, for example,

Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp.,

Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp.,

Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp.,

Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogorma spp.; of the order Orthoptera, for example,

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp.,

Periplaneta spp. and Schistocerca spp.; of the order Isoptera, for example,

Reticulitermes spp.; of the order Psocoptera, for example,

Liposcelis spp.; of the order Anoplura, for example,

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; of the order Mallophaga, for example,

Damalinea spp. and Trichodectes spp.; of the order Thysanoptera, for example,

Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and

Scirtothrips aurantii; of the order Heteroptera, for example,

Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp.,

Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis,

Scotinophara spp. and Triatoma spp.; of the order Homoptera, for example,

Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp.,

Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium,

Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum,

Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp.,

Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp.,

Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp.,

Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp.,

Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri; of the order Hymenoptera, for example,

Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma,

Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.; of the order Diptera, for example,

Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster,

Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp.,

Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp.,

Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; of the order Siphonaptera, for example,

Ceratophyllus spp. and Xenopsylla cheopis; of the order Thysanura, for example,

Lepisma saccharina; of the order Acarina, for example,

Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp.,

Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp.,

Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora,

Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp.,

Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.

With the compounds according to the invention it is possible to control, i.e. to inhibit or destroy, pests of the mentioned type occurring especially on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forestry, or on parts of such plants, such as the fruit, blossom, leaves, stems, tubers or roots, while some of the parts of the plants which grow later are also protected against those pests.

Target crops are especially cereals, such as wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, such as pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries, or berries, for example strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans and groundnuts; cucumber plants, such as marrows, cucumber and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruit, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus,

cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocados, cinnamon and camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.

The compounds of the invention are suitable especially for controlling Boophilus microplus, Nilaparvata lugens, Panonychus ulmi and Tetranychus urticae in crops of vegetables, fruit and rice.

Further areas of use of the compounds according to the invention are the protection of stored goods and stocks and materials, and also in the hygiene sector, especially the protection of domestic animals and productive livestock against pests of the mentioned type.

The invention therefore relates also to pesticides, such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising - at least - one of the compounds of the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances.

The active ingredient is used in those compositions in pure form, a solid active ingredient, for example, in a specific particle size, or preferably together with - at least - one of the adjuvants customary in formulation technology, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).

Suitable solvents are, for example: optionally partially hydrogenated aromatic hydro¬ carbons, preferably the fractions of alkylbenzenes containing 8 to 12 carbon atoms, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cyclo- aliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols, such as ethanol, propanol or butanol, glycols and their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, vegetable oils or epoxidised vegetable oils, such as rape oil, castor oil, coconut oil or soybean oil or epoxidised rape oil, castor oil, coconut oil or soybean oil, and silicone oils.

The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acids or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, such as pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are calcite or sand. In addition, a great number of granulated materials of inorganic or organic nature can be used, especially dolomite or pulverised plant residues.

Depending on the nature of the compound to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants or mixtures of surfactants having good emulsifying, dispersing and wetting properties. The surfactants listed below are to be regarded merely as examples; many more surfactants customarily employed in formulation technology and suitable for use according to the invention are described in the relevant literature.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cyclo- aliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydro¬ carbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. Further suitable non-ionic surfactants are water-soluble adducts of polyethylene oxide with poly¬ propylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Representative examples of non-ionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy- polyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as substituent, at least one C ₈ -C ₂₂ alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates. Examples are stearyltrimethyl- ammonium chloride and benzyl-di(2-chloroethyl)ethylammonium bromide.

Both water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants. Suitable soaps are the alkali metal salts, alkaline earth metal salts and unsubstituted or substituted ammonium salts of higher fatty acids (C ₁₀ -C ₂₂ ), e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tall oil; mention may also be made of fatty acid methyltaurin salts. More frequently, however, synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkyl- arylsulfonates. The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and generally contain a C ₈ -C ₂₂ alkyl radical, which also includes the alkyl moiety of acyl radicals; there may be mentioned by way of example the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing approximately 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.

The compositions usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of active ingredient, and 1 to 99.9 %, preferably 5 to 99.9 %, of - at least - one solid or liquid adjuvant, it generally being possible for 0 to 25 , preferably 0.1 to 20 %, of the composition to be surfactants (in each case percentages are by weight). Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations which have considerably lower active ingredient concentrations. Preferred formulations have especially the following composition (throughout, percentages are by weight):

Emulsifiable concentrates: active ingredient: 1 to 90 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % solvent: 5 to 98 %, preferably 70 to 85 %

Dusts: active ingredient: 0.1 to 10 , preferably 0.1 to 1 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %

Suspension concentrates: active ingredient: 5 to 75 , preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 %

Wettable powders: active ingredient: 0.5 to 90 %, preferably 1 to 80 % surfactant: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 99 %, preferably 15 to 98 %

Granules: active ingredient: 0.5 to 30 %, preferably 3 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The activity of the compositions according to the invention can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticidal active ingredients. Examples of suitable additional active ingredients include representatives of the following classes of compounds: organophosphorus compounds, nitrophenols and derivatives, formamidines, acylureas, carbamates, pyrethroids, nitroenamines and derivatives, pyrroles, thioureas and derivatives, chlorinated hydrocarbons, and Bacillus thuringiensis preparations. The compositions according to the invention may also comprise further solid or liquid adjuvants, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil, rape oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilisers or other active ingredients for obtaining special effects, for example acaricides, bactericides, fungicides, nematicides, molluscicides or selective herbicides.

The compositions according to the invention are prepared in known manner, in the absence of adjuvants, for example by grinding, sieving and/or compressing a solid active ingredient or mixture of active ingredients, for example to a specific particle size, and in the presence of at least one adjuvant, for example by intimately mixing and/or grinding the

active ingredient or mixture of active ingredients with the adjuvant(s). The invention relates also to those processes for the preparation of the compositions according to the invention and to the use of the compounds I in the preparation of those compositions.

The invention relates also to the methods of application of the compositions, i.e. the methods of controlling pests of the mentioned type, such as spraying, atomising, dusting, coating, dressing, scattering or pouring, which are selected in accordance with the intended objectives and prevailing circumstances, and to the use of the compositions for controlling pests of the mentioned type. Typical rates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, of active ingredient. The rates of application per hectare are generally from 1 to 2000 g of active ingredient per hectare, especially from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.

A preferred method of application in the area of plant protection is application to the foliage of the plants (foliar application), the number of applications and the rate of application depending on the risk of infestation by the pest in question. However, the active ingredient can also penetrate the plants through the roots (systemic action) if the locus of the plants is impregnated with a liquid formulation or if the active ingredient is incorporated in solid form into the locus of the plants, for example into the soil, e.g. in granular form (soil application). In paddy rice crops, such granules may be applied in metered amounts to the flooded rice field.

The compositions according to the invention are also suitable for protecting plant propagation material, e.g. seed material, such as fruit, tubers or grains, or plant cuttings, from animal pests. The propagation material can be treated with the formulation before planting: seed, for example, can be dressed before being sown. The compounds of the invention can also be applied to grains (coating), either by impregnating the grains with a liquid formulation or by coating them with a solid formulation. The formulation can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing. The invention relates also to those methods of treating plant propagation material and to the plant propagation material thus treated.

The following Examples are intended to illustrate the invention. They do not limit the invention. Temperatures are given in degrees Celsius. The abbreviation "c-" stands for "cyclo-".

Preparation examples

Example PI: N-[(2,2-difluorocyclopropyl)acetyl]benzenesulfonamide (Table 1,

Compound No. 1.1).

A mixture of 1.5 g of (2,2-difluorocyclopropyl)acetyl chloride and 1.25 g of benzene- sulfonamide is heated to 140° (bath temperature). A melt is formed which is stirred for 4 hours at 140°. After cooling, the reaction product is precipitated by the addition of hexane, filtered with suction and washed with hexane. The crude product is dissolved at 70° in a small amount of toluene and hexane is added until crystallising-out begins, yielding the title compound in the form of a colourless powder that melts at from 97 to 99°.

Example P2: The other compounds listed in Tables 1 and 2 can be prepared in a manner analogous to that described in Example PI. In the "Physical data" column of those Tables the temperatures given denote the melting point of the compound in question and "n _D ^τ " is the refractive index of the compound in question at the temperature T°C.

Table 1

Physical data

97-99°

128-130°

130-132°

100-102°

99-100°

3 95-98° 3 103-105° 3 93-95° 3 n _D ²⁶ =1.5110

97-99°

137-138°

114-116°

148-150°

128-130° 126-128°

109-110°

93-96°

134-135°

143-144°

90-92°

102-103° oil

168-169°

n _D ²⁴ =1.5052

24_

"D 1.4590 wax

100 -N(CH ₃ )C ₆ H ₄ C1(4) 101 -N(CH ₃ )-n-C ₁₀ H _2j 102 -N(CH ₃ )CH ₂ CH ₂ OCH ₃ 103 -N(CH ₃ )-c-C ₃ H ₅ 104 -N(CH ₃ )C ₆ H ₃ C1 ₂ (3,4) 105 -N(C ₂ H ₅ )C ₆ H ₄ CF ₃ (3) 106 C ₆ H ₄ OC ₆ H ₅ (4) 107 C ₆ H ₄ SCH ₃ (4) 108 C ₆ H ₄ SOCH ₃ (4) 109 C ₆ H ₄ SO ₂ CH ₃ (4) 110 C ₆ F ,SO ₂ NH ₂ (4) 111 -N(CH ₃ )CH ₂ CF ₃ 112 -N(n-C ₆ H _j3 ) ₂ 113 -N(CH ₃ )C ₆ H ₄ CF ₃ (3) 114 -N(CH ₃ )C ₆ H ₄ CN(4) 115 -N(CH ₃ )C ₆ H ₄ NO ₂ (4) 116 -N(CH ₃ )C ₆ H ₄ OCH ₃ (4) 117 -N(C ₆ H ₅ ) ₂ 118 -N(n-C ₈ H _j7 ) ₂ 119 -N(n-C ₅ H _{j j} ) ₂ 120 -N(CH ₃ )CH ₂ CH ₂ CN 121 -N(H)C ₆ H ₃ C1 ₂ (3,4) 122 -OC ₆ H ₅ 123 -OC ₆ H ₄ Cl(4) 124 -OC ₆ H ₄ CH ₃ (4) 125 -OC ₆ H ₄ OCH ₃ (4) 126 -N(H)-c-C ₆ H _{j j} 127 -N(H)C ₆ H ₄ C1(4) 128 -N(H)C ₆ H ₄ CF ₃ (3) 129 -N(H)C ₆ H ₃ (CF ₃ ) ₂ (3,5) 130 4-ethoxycarbonylpiperid- 1 -yl 131 3-ethoxycarbonylpiperid-l-yl 132 4-phenylpiperazin-l-yl 133 4-(4-F-phenyl)-piperazin-l-yl 134 4-(2-CH ₃ -phenyl)-piperazin-l-yl 135 3,3-dimethylpiperid-l-yl

1.136 2,6-dimethylpiρerid- 1 -yl 1.137 l,2,3,4-tetrahydroisoquinolin-2-yl 1.138 1 ,2,3,4-tetrahydroquinolin-2-yl 1.139 indolin-1-yl 1.140 4-(2-OCH ₃ -phenyl)-piperazin-l-yl 1.141 4-(4-nitrophenyl)-piperazin-l-yl 1.142 4-benzylpiperazin- 1 -yl 1.143 4-(2-pyridyl)-piperazin- 1 -yl 1.144 4-(3,4-Cl ₂ -phenyl)-piperazin-l-yl 1.145 4-(4-OCH ₃ -phenyl)-piperazin-l-yl 1.146 4-ethylpiperazin- 1 -yl 1.147 pyrrol- 1-yl

Table 2

n Physical data

3 3 3 3

2.137 l,2,3,4-tetrahydroisoquinolin-2-yl 2.138 1 ,2,3,4-tetrahydroquinolin-2-yl 2.139 indolin-1-yl 2.140 4-(2-OCH ₃ -phenyl)-piperazin- 1 -yl 2.141 4-(4-nitrophenyl)-piperazin-l-yl 2.142 4-benzylpiperazin- 1 -yl 2.143 4-(2-pyridyl)-piperazin-l-yl 2.144 4-(3,4-Cl ₂ -phenyl)-piperazin-l-yl 2.145 4- (4-OCH ₃ -phenyl)-piperazin- 1 -yl 2.146 4-ethylpiperazin- 1 -yl 2.147 pyrrol- 1-yl

Example P3: 4-aminosulfonvl-2.6-dimethylmoφholine (Table 3, Compound no. 3.01) A mixture of 115 g of 2,6-dimethylmorpholine and 115 g of sulfamide is, after addition of 200 ml of water, boiled under reflux for 5 hours, cooled, acidified with dilute hydrochloric acid and filtered off. The resulting product is recrystallised in water to yield the title compound in the form of a white powder having a melting point of 135-137°.

Example P4: The other compounds listed in Table 3 can be prepared in a manner analog¬ ous to that described in Example P3. In the "Physical data" column of that Table the temperatures given denote the melting point of the compound in question and "n _D ^τ " is the refractive index of the compound in question at the temperature T°C.

Table 3

Physical data

135-137° 160-162° 107-108° 121-122°

171-172°

51-52° n _D ²⁷ =1.4657

79-81° n _D ²³ =1.4760

164-165°

78-79°

88-89°

101-102°

104-106 ^c

178-179°

3.29 3-ethoxycarbonylpiperid-l-yl

3.30 -N(CH ₃ ) ₂ 95-96°

3.31 -N(C ₂ H ₅ ) ₂ 43-44°

3.32 -N(n-C ₃ H ₇ ) ₂

3.33 -N(CH ₃ )-n-C ₄ H ₉

3.34 -N(CH ₃ )-c-C ₆ H _{j j}

3.35 -N(CH ₃ )-c-C ₃ H ₅

3.36 -N(CH ₃ )C ₆ H ₄ OCH ₃ (4)

3.37 -N(C ₆ H ₅ ) ₂

3.38 -N(n-C ₈ H _j7 ) ₂

3.39 -N(n-C ₅ H _{j j} ) ₂

3.40 -N(CH ₃ )CH ₂ CH ₂ CN

3.42 -N(H)C ₆ H ₄ C1(4)

3.43 -N(H)C ₆ H ₃ C1 ₂ (3,4)

3.44 -N(H)C ₆ H ₄ CF ₃ (3)

3.45 -N(H)C ₆ H ₃ (CF ₃ ) ₂ (3,5)

3.46 4-(4-F-phenyl)-piperazin-l-yl

3.47 4-(2-CH ₃ -phenyl)-piperazin-l-yl

3.48 -N(CH ₃ )CH ₂ CF ₃

3.49 3,3-dimethylρiperid-l-yl

3.50 2,6-dimethylpiperid-l-yl

3.51 1 ,2,3,4-tetrahydroisoquinolin-2-yl

3.52 1 ,2,3,4-tetrahydroquinolin-2-yl

3.53 indolin-1-yl

3.54 4-(2-OCH ₃ -phenyl)-piperazin-l-yl 155-157°

3.55 4-(4-nitrophenyl)-piperazin-l-yl

3.56 4-benzylpiperazin-l-yl

3.57 4-(2-pyridy')-piperazin-l-yl

3.58 4-(3,4-Cl ₂ -phenyl)-piperazin-l-yl

3.59 4-(4-OCH ₃ -phenyl)-piperazin-l-yl

3.60 4-ethylpiperazin-l-yl

3.61 pyrrol- 1-yl

Formulation Exam les throu hout ercenta es are b wei ht

The finely ground active ingredient is mixed with the adjuvants, giving an emulsifiable concentrate from which emulsions of any desired concentration can be prepared by dilution with water.

Example F2: Solutions a) b) c) d) compound No. 1.3 80 % 10 % 5 % 95 % ethylene glycol monomethyl ether 20 % - polyethylene glycol

(mol. wt. 400) - 70 % -

N-methylpyrrolid-2-one - 20 % - epoxidised coconut oil - - 1 % 5 % petroleum fraction

(boiling range 160-190°C) - - 94 % -

The finely ground active ingredient is mixed with the adjuvants, giving a solution that is suitable for application in the form of microdrops.

The active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier mixture, and the solvent is evaporated off in vacuo.

Ready-for-use dusts are obtained by mixing the active ingredient with the carriers.

The active ingredient is mixed with the adjuvants and the mixture is ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

Example F6: Emulsifiable concentrate compound No. 1.7 10 % octylphenol polyethylene glycol ether

(4-5 mol of ethylene oxide) 3 % calcium dodecylbenzenesulfonate 3 % castor oil polyethylene glycol ether

(36 mol of ethylene oxide) 4 % cyclohexanone 30 % xylene mixture 50 %

The finely ground active ingredient is mixed with the adjuvants, giving an emulsifiable concentrate from which emulsions of any desired concentration can be prepared by dilution with water.

Example F7: Dusts compound No. 1.6 talcum kaolin - 92 %

Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill.

Example F8: Extruder granules compound No. 1.8 10 % sodium lignosulfonate 2 % carboxymethylcellulose 1 % kaolin 87 %

The active ingredient is mixed with the adjuvants, and the mixture is ground, moistened with water, extruded and granulated, and the granules are then dried in a stream of air.

Example F9: Coated granules compound No. 1.9 3 % polyethylene glycol (mol. wt. 200) 3 % kaolin 94 %

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol, affording non-dusty coated granules.

carboxymethylcellulose 1 % aqueous formaldehyde solution (37 %) 0.2 % aqueous silicone oil emulsion (75 %) 0.8 % water 32 %

The finely ground active ingredient is mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

Biological Examples (throughout, percentages are by weight unless otherwise indicated)

A. Insecticidal action

Example B l: Action against Nilaparvata lugens

Rice plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound.

After the spray coating has dried, the rice plants are populated with plant hopper larvae in the 2nd and 3rd stages. Evaluation is made 21 days later. The percentage reduction in the population (% activity) is determined by comparing the number of surviving plant hoppers on the treated plants with that on untreated plants.

Compounds of Tables 1 and 2 exhibit good activity in this test. In particular, Compound

No. 1.2 is more than 80 % effective.

B. Acaricidal action

Example B2: Action against Boophilus microplus

Adult female ticks which are replete with blood are affixed to a PVC plate and covered with a cotton wool swab. 10 ml of an aqueous test solution comprising 125 ppm of test compound are then poured over the test insects The cotton wool swab is then removed and the ticks are incubated for 4 weeks until place. The action manifests itself ^" either as mortality or sterility of the females or as ovicidal action in the eggs.

Compounds of Tables 1 and 2 exhibit good activity in this test. In particular, Compounds

No. 1.2, 1.8 and 1.11 are more than 80 % effective.

Example B3: Action against Tetranychus urticae

Young bean plants are populated with a mixed population of Tetranychus urticae and one day later are sprayed with an aqueous emulsion comprising 400 ppm of test compound. The plants are then incubated for 6 days at 25° and then evaluation is made. The percen¬ tage reduction in the population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on the untreated plants. The compounds of Tables 1 and 2 exhibit good activity in this test. In particular, Compounds No. 1.1, 1.2 and 1.11 are more than 80 % effective.

Example B4: Action against Panonychus ulmi

Apple seedlings are populated with adult females of Panonychus ulmi and after 7 days the seedlings are sprayed to drip point with an aqueous emulsion comprising 400 ppm of test compound and then cultivated in a greenhouse. Evaluation is made 14 days later. The percentage reduction in the population (% activity) is determined by comparing the number of dead spider mites on the treated plants with that on untreated plants. Compounds of Tables 1 and 2 exhibit good activity in this test. In particular, Compounds No. 1.1, 1.2 and 1.11 are more than 80 % effective.